CN103779621A - Service life prolonging liquid of lead-acid storage battery and preparation method thereof - Google Patents
Service life prolonging liquid of lead-acid storage battery and preparation method thereof Download PDFInfo
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- CN103779621A CN103779621A CN201410010798.8A CN201410010798A CN103779621A CN 103779621 A CN103779621 A CN 103779621A CN 201410010798 A CN201410010798 A CN 201410010798A CN 103779621 A CN103779621 A CN 103779621A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4242—Regeneration of electrolyte or reactants
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/08—Selection of materials as electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/12—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a service life prolonging liquid of a lead-acid storage battery and a preparation method thereof. The service life prolonging liquid of the lead-acid storage battery is a water-phase system; the service life prolonging liquid of the lead-acid storage battery comprises the following components in percentage by mass (100%): 0.03-30% of carbon nanomaterials, 0-20% of inorganic salt and 0.01-10% of organic additives and rest of water. The service life prolonging liquid of the lead-acid storage battery is good in effect and is capable of effectively prolonging the service life of the lead-acid storage battery and improving capacity of the waste lead-acid storage battery. The preparation method of the service life prolonging liquid of the lead-acid storage battery is simple in process, so that the service life prolonging liquid of the lead-acid storage battery has an attractive application prospect in the field of the lead-acid storage batteries.
Description
Technical field:
The invention belongs to the performance and the waste lead acid battery reparation field that promote new lead-acid battery, be specifically related to a kind of lead-acid battery and increase longevity liquid and preparation method thereof.
Background technology:
Lead-acid battery is historical the longest secondary cell, have memory-less effect, electric energy efficiency up to 60%, the advantage such as high temperature performance is good, single-unit voltage is high, high magnification power generation performance, and with its high cost performance be still in the world most widely used rechargeable battery (Han Shiliang. Harbin railway science and technology, 2012,03:45-46).At present, lead-acid battery is indispensable product in social production business activities and the mankind, in storage battery field, still occupies very important status also, and the pollution that reduces fuel-engined vehicle and fuel motorcycle has also been made to huge contribution.But the useful life of lead acid accumulator is shorter, thereby a large amount of discarded lead acid accumulators in having eliminated fuel oil pollution, are produced, if lead acid accumulator can not get effectively processing after discarded, by serious environment pollution and soil, its destructiveness has certain irreversibility, the blood lead that takes place frequently the in recent years event that exceeds standard, its troublemaker be lead acid accumulator (Sun Xiuyan. People's Daily, on May 5th, 2011, the 020th edition: 1-3).Therefore, exploitation can greatly extend the useful life of lead-acid battery and effectively process the new technology of discarded lead-acid battery, has very important social effect, and can create larger economic benefit.
Lead-acid battery in use decline gradually because the failure modes such as negative pole sulfation, anode plate grid corrosion cause its chemical property (Ru Baoxing. technology and exploitation, 2005,08:32-33).Be generally 2-3 the designed life of common lead acid accumulator, but its actual use usually only has 1 year or shorter time, be 7-15 the designed life of maintenance-free lead accumulator, but be also significantly shorter than expected service life its actual life.And the consumption of plumbic acid is extremely huge, developing rapidly of energy storage industry needs the support of continuous new technology, extends the useful life of product by the mode of Material Addition, will become the very cost-effective means of one.If can extend the life-span of lead-acid battery or the old lead-acid battery of expense can be repaired by some rational means, extended to 50% the useful life of lead-acid battery product, in fact be equivalent to increase by 50% output, this is a kind of technology of low-cost high-efficiency benefit, and industrialization prospect is very optimistic.
Summary of the invention:
The object of this invention is to provide the extraordinary lead-acid battery of a kind of effect and increase longevity liquid and preparation method thereof, this preparation method has simple for process, with low cost, high repeatability and other advantages, shows huge application prospect in the reparation of waste lead acid battery and in extending the application such as the useful life of new lead-acid battery.
Lead-acid battery of the present invention increases longevity liquid, it is characterized in that, it is aqueous phase system that described lead-acid battery increases longevity liquid, by gross mass mark 100%, comprises carbon nanomaterial 0.03～30%, inorganic salts 0～20% and organic additive 0.01～10%, and surplus is water;
Described carbon nanomaterial can be a kind of, two kinds or several composition in the materials such as carbon nano-tube, carbon nano-fiber, nano-carbon powder, acetylene black or Graphene;
Described inorganic salts can be a kind of, two kinds or several compositions in sulfate, nitrate or chloride etc.;
Described organic additive is a kind of, two kinds or several composition in poly(ethylene oxide), polyvinyl alcohol, polyvinylpyrrolidone, polycaprolactone, methyl iso-butyl ketone (MIBK), methyl alcohol, ethanol, ethylene glycol, glycerol, isobutanol, TBAB, 4-butyl ammonium hydrogen sulfate or tetrabutylammonium iodide.
Lead-acid battery of the present invention increases longevity liquid to be prepared by the following method, and the method comprises the following steps:
The formula that increases longevity liquid by above-mentioned lead-acid battery weighs each component, and carbon nanomaterial is carried out to surface treatment, is then scattered in aqueous phase system, then adds successively inorganic salts and organic additive, stirs and carries out obtaining lead-acid battery increasing longevity liquid after ultrasonic processing;
Described carries out surface treatment by carbon nanomaterial, its surface treatment is heat treatment, acid treatment or ammonia corrosion processing, described heat treatment is in air, nitrogen, hydrogen, carbon dioxide or steam atmosphere, under 600～1050 ℃ of conditions, processes 0.1～7 hour; Described acid treatment is the mixture that adopts a kind of, two kinds or several acid in sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, under 30～90 ℃ of conditions, processes 0.1～6 hour; Described ammonia corrosion processing is in ammonia or the mixed atmosphere that contains ammonia, under 600～1100 ℃ of conditions, processes 0.1～8 hour.
Described sulfate can be sodium sulphate, potassium sulfate, copper sulphate, magnesium sulfate, aluminum sulfate, alum, zinc sulfate, ferrous sulfate, ferric sulfate, nickelous sulfate etc.
Described nitrate can be sodium nitrate, potassium nitrate, calcium nitrate, magnesium nitrate, aluminum nitrate, zinc nitrate, magnesium nitrate, copper nitrate, ferric nitrate, nickel nitrate, cobalt nitrate, manganese nitrate, cerous nitrate, lanthanum nitrate etc.
Described chloride can be sodium chloride, potassium chloride, calcium chloride, copper chloride, alchlor, zinc chloride, magnesium chloride, frerrous chloride, iron chloride, nickel chloride, cobalt chloride, manganese chloride etc.
Sulfuric acid, nitric acid, phosphoric acid and hydrochloric acid in described acid treatment, the preferably concentrated sulfuric acid, red fuming nitric acid (RFNA), SPA and concentrated hydrochloric acid or the wherein nitration mixture of two kinds of concentrated acids, process the preferably nitration mixture of the concentrated sulfuric acid and red fuming nitric acid (RFNA), the preferred 3:1 of volume proportion of the two if adopt nitration mixture.
The described mixed atmosphere that contains ammonia, preferred nitrogen/ammonia gas mixture, the volume proportion of gaseous mixture preferably 40%/60%.
Described is ultrasonic, and its ultrasound condition can be under 25-90 ℃ of condition, ultrasonic processing 0.1-8h.
Preferably, it is aqueous phase system that described lead-acid battery increases longevity liquid, by gross mass mark 100%, comprise carbon nano-tube 2%, Graphene 2%, carbon nano-fiber 5%, carbon nano powder 18%, sodium sulphate 2%, sodium nitrate 1.5% and TBAB 8%, surplus is water, by carbon nano-tube, Graphene, Nano carbon fibers peacekeeping carbon nano powder, the red fuming nitric acid (RFNA) that is 3:1 by volume ratio and the nitration mixture of red fuming nitric acid (RFNA), under 80 ℃ of conditions, process 1.5 hours, after processing, solution is cleaned with clear water, under 110 degree conditions, dry 3 hours, again by the carbon nano-tube after drying, Graphene, Nano carbon fibers peacekeeping carbon nano powder sample dispersion is in the aqueous solution, add successively sodium sulphate, sodium nitrate and TBAB, at ambient temperature, agitating heating 2 hours, then at room temperature ultrasonic processing 4 hours, ultrasonic power 300W, obtain lead-acid battery and increase longevity liquid.
Lead-acid battery of the present invention increases longevity liquid, it is effective, can effectively extend the useful life of new lead-acid battery and the capacity of raising waste lead acid battery, and this lead-acid battery increases the preparation method of longevity liquid, technique is simple, and therefore the present invention has very tempting application prospect in lead-acid battery field.
Accompanying drawing explanation:
Fig. 1 is that lead-acid battery of the present invention increases the repair process schematic diagram of longevity liquid to plumbic acid old and useless battery.And the basic process that increases the test of longevity liquid to new lead-acid battery performance impact is, first carry out charge-discharge test several times, obtain the initial capacity of battery; Then, add lead-acid battery to increase longevity liquid, carry out charge-discharge test several times, obtain the capacity of battery, relatively add the variation of lead-acid battery increasing longevity liquid front and back battery capacity.
Embodiment:
Following examples are to further illustrate of the present invention, rather than limitation of the present invention.
Embodiment 1:
It is aqueous phase system that the lead-acid battery of the present embodiment increases longevity liquid, by gross mass mark 100%, comprises carbon nano-tube 0.03%, sodium sulphate 15%, zinc nitrate 3%, potassium chloride 2% and polyvinyl alcohol 0.01%, and surplus is water.Carbon nano-tube is placed in to glass flask, adds the nitration mixture (volume proportion is 2:1) of the concentrated sulfuric acid and concentrated hydrochloric acid, under 50 ℃ of conditions, process carbon nanotube powder 6 hours, after processing, solution is cleaned with clear water, under 110 degree conditions, dry 3 hours.Then, the carbon nano-tube sample dispersion after drying, in the aqueous solution, is added to sodium sulphate, zinc nitrate, potassium chloride and polyvinyl alcohol successively, under 60 degree, agitating heating 4 hours, then at room temperature ultrasonic processing 0.1 hour, ultrasonic power 200W, obtains lead-acid battery and increases longevity liquid sample.
According to shown in Fig. 1, waste lead acid battery is repaired, repair process is: waste lead acid battery is discharged, after having discharged, then add lead-acid battery to increase longevity liquid, charging, battery is full of, discharging current is set and discharges again, after the electric discharge that repeatedly circulates, after battery capacity is stable, can obtain stable battery capacitor, i.e. the reparation of waste lead acid battery completes.
The test result that the lead-acid battery of the present embodiment is increased to longevity liquid is as shown in table 1 below:
Table 1
Result shows, the capacity that increases the waste lead acid battery after longevity liquid reparation through the lead-acid battery of the present embodiment improves approximately 4%.
Embodiment 2:
It is aqueous phase system that the lead-acid battery of the present embodiment increases longevity liquid, by gross mass mark 100%, comprises Graphene 5%, potassium sulfate 5% and 4-butyl ammonium hydrogen sulfate 10%, and surplus is water.Ammonia (NH by Graphene at 600 ℃
3) middle processing 8 hours, then Graphene after treatment is dispersed in water, add successively potassium sulfate and 4-butyl ammonium hydrogen sulfate, under 60 degree, agitating heating 2 hours, then at room temperature ultrasonic processing 8 hours, ultrasonic power 400W, obtains lead-acid battery and increases longevity liquid sample.The method of testing of the repairing performance to plumbic acid increasing longevity liquid is completely with described in embodiment 1.The test result that the lead-acid battery of the present embodiment is increased to longevity liquid is as shown in table 2 below:
Table 2
Result shows, the capacity that increases the waste lead acid battery after longevity liquid reparation through the lead-acid battery of the present embodiment improves approximately 4%.
Embodiment 3:
It is aqueous phase system that the lead-acid battery of the present embodiment increases longevity liquid, by gross mass mark 100%, comprises carbon nano-fiber 20%, potassium sulfate 1%, magnesium nitrate 5% and tetrabutylammonium iodide 3%, and surplus is water.Carbon nano-fiber is placed in to glass flask, then uses the nitration mixture (volume proportion is 3:1) of the concentrated sulfuric acid and red fuming nitric acid (RFNA) to process carbon nano-fiber 3 hours under 40 ℃ of conditions, after processing, solution is cleaned with clear water, under 110 degree conditions, dry 3 hours.Again by dry after carbon nano-fiber sample dispersion in the aqueous solution, add successively potassium sulfate, magnesium nitrate and tetrabutylammonium iodide, at ambient temperature, agitating heating 1 hour, then ultrasonic processing 4 hours, ultrasonic power 300W, obtains lead-acid battery and increases longevity liquid sample.The method of testing of the repairing performance to lead-acid battery increasing longevity liquid is completely with described in embodiment 1.The test result that the lead-acid battery of the present embodiment is increased to longevity liquid is as shown in table 3 below:
Table 3
Result shows, the capacity that increases the waste lead acid battery after longevity liquid reparation through the lead-acid battery of the present embodiment improves approximately 11%.
Embodiment 4:
It is aqueous phase system that the lead-acid battery of the present embodiment increases longevity liquid, by gross mass mark 100%, comprises carbon nano powder 20%, alum 0.1%, cerous nitrate 1%, greening nickel 0.02%, poly(ethylene oxide) 2% and dodecyl sodium sulfate 0.01%, and surplus is water.Nitration mixture (volume proportion is 5:1) by carbon nano powder with red fuming nitric acid (RFNA) and SPA is processed 5 hours under 70 ℃ of conditions, after processing, solution cleaned with clear water, and under 110 degree conditions, dry 3 hours.Again by dry after carbon nano powder sample dispersion in the aqueous solution, add successively alum, cerous nitrate, greening nickel, poly(ethylene oxide) and dodecyl sodium sulfate, under 70 degree conditions, agitating heating 5 hours, then at room temperature ultrasonic processing 1 hour, ultrasonic power 200W, obtains lead-acid battery and increases longevity liquid sample.The method of testing of the repairing performance to lead-acid battery increasing longevity liquid is completely with described in embodiment 1.The test result that the lead-acid battery of the present embodiment is increased to longevity liquid is as shown in table 4 below:
Table 4
Result shows, the capacity that increases the waste lead acid battery after longevity liquid reparation through the lead-acid battery of the present embodiment improves approximately 14%.
Embodiment 5:
It is aqueous phase system that the lead-acid battery of the present embodiment increases longevity liquid, by gross mass mark 100%, comprises carbon nano powder 20%, alum 0.1%, cerous nitrate 1%, nickel chloride 0.02%, poly(ethylene oxide) 2% and dodecyl sodium sulfate 0.01%, and surplus is water.First by carbon nano powder in carbon dioxide atmosphere, under 600 degree conditions, process 7 hours.Again by carbon nano powder sample dispersion in the aqueous solution, add successively alum, cerous nitrate, nickel chloride, poly(ethylene oxide) and dodecyl sodium sulfate, under 70 degree conditions, agitating heating 5 hours, then at room temperature ultrasonic processing 1 hour, ultrasonic power 200W, obtains lead-acid battery and increases longevity liquid sample.The method of testing of the repairing performance to lead-acid battery increasing longevity liquid is completely with described in embodiment 1.The test result that the lead-acid battery of the present embodiment is increased to longevity liquid is as shown in table 5 below:
Table 5
Result shows, the capacity that increases the waste lead acid battery after longevity liquid reparation through the lead-acid battery of the present embodiment improves approximately 19%.
Embodiment 6:
It is aqueous phase system that the lead-acid battery of the present embodiment increases longevity liquid, by gross mass mark 100%, comprise carbon CNT (carbon nano-tube) 25%, carbon nano-fiber 5%, alum 0.1%, cerous nitrate 1%, nickel chloride 0.02%, poly(ethylene oxide) 2% and dodecyl sodium sulfate 0.01%, surplus is water.By CNT (carbon nano-tube) and carbon nano-fiber, with the nitration mixture (volume proportion is 1:1) of the concentrated sulfuric acid and red fuming nitric acid (RFNA), under 90 ℃ of conditions, process 1 hour, after processing, solution is cleaned with clear water, under 110 degree conditions, dry 3 hours.Again by dry after CNT (carbon nano-tube) and carbon nano-fiber sample dispersion in the aqueous solution, add successively alum, cerous nitrate, nickel chloride, poly(ethylene oxide) and dodecyl sodium sulfate, under 60 degree conditions, agitating heating 4 hours, then at room temperature ultrasonic processing 2 hours, ultrasonic power 200W, obtains lead-acid battery and increases longevity liquid sample.The method of testing of the repairing performance to lead-acid battery increasing longevity liquid is completely with described in embodiment 1.The test result that the lead-acid battery of the present embodiment is increased to longevity liquid is as shown in table 6 below:
Table 6
Result shows, the capacity that increases the waste lead acid battery after longevity liquid reparation through the lead-acid battery of the present embodiment improves approximately 20%.
Embodiment 7:
It is aqueous phase system that the lead-acid battery of the present embodiment increases longevity liquid, by gross mass mark 100%, comprises carbon CNT (carbon nano-tube) 20%, carbon nano-fiber 5%, ethanol 0.5%, polyvinylpyrrolidone 3% and poly(ethylene oxide) 1%, and surplus is water.By CNT (carbon nano-tube) and carbon nano-fiber, at the ammonia (NH of 1100 ℃
3) middle processing 0.1 hour.Again by the CNT (carbon nano-tube) after heat treatment and carbon nano-fiber sample dispersion in the aqueous solution, add successively ethanol, polyvinylpyrrolidone and poly(ethylene oxide), under 60 degree conditions, agitating heating 4 hours, then at room temperature ultrasonic processing 2 hours, ultrasonic power 200W, obtains lead-acid battery and increases longevity liquid sample.The method of testing of the repairing performance to lead-acid battery increasing longevity liquid is completely with described in embodiment 1.The test result that the lead-acid battery of the present embodiment is increased to longevity liquid is as shown in table 7 below:
Table 7
Result shows, the capacity that increases the waste lead acid battery after longevity liquid reparation through the lead-acid battery of the present embodiment improves approximately 12%.
Embodiment 8:
It is aqueous phase system that the lead-acid battery of the present embodiment increases longevity liquid, by gross mass mark 100%, comprises carbon CNT (carbon nano-tube) 25%, carbon nano-fiber 5%, sodium sulphate 3%, ethylene glycol 1%, isobutanol 1%, methyl iso-butyl ketone (MIBK) 1%, polyvinylpyrrolidone 3%, and surplus is water.First by CNT (carbon nano-tube) and carbon nano-fiber in air atmosphere, under 1050 degree conditions, process 0.1 hour.Again by CNT (carbon nano-tube) and carbon nano-fiber sample dispersion in the aqueous solution, add successively sodium sulphate, ethylene glycol, isobutanol, methyl iso-butyl ketone (MIBK), polyvinylpyrrolidone, under 90 degree conditions, agitating heating 4 hours, then ultrasonic processing 2 hours under 90 degree conditions, ultrasonic power 200W, obtains lead-acid battery and increases longevity liquid sample.The method of testing of the repairing performance to increasing longevity liquid is completely with described in embodiment 1.The test result that the lead-acid battery of the present embodiment is increased to longevity liquid is as shown in table 8 below:
Table 8
Result shows, the capacity that increases the waste lead acid battery after longevity liquid reparation through the lead-acid battery of the present embodiment improves approximately 12%.
Embodiment 9:
It is aqueous phase system that the lead-acid battery of the present embodiment increases longevity liquid, by gross mass mark 100%, comprises Graphene 2%, carbon nano-fiber 20%, carbon nano powder 4.5%, alum 1.8%, magnesium nitrate 4.3% and tetrabutylammonium iodide 5%, and surplus is water.By Graphene, Nano carbon fibers peacekeeping carbon nano powder, with the nitration mixture (volume proportion is 3:1) of red fuming nitric acid (RFNA) and red fuming nitric acid (RFNA), under 90 ℃ of conditions, process 0.5 hour, after processing, solution is cleaned with clear water, under 110 degree conditions, dry 3 hours.Again by Graphene, Nano carbon fibers peacekeeping carbon nano powder sample dispersion after drying in the aqueous solution, add successively alum, magnesium nitrate and tetrabutylammonium iodide, at ambient temperature, agitating heating 2 hours, then at room temperature ultrasonic processing 3 hours, ultrasonic power 300W, obtains lead-acid battery and increases longevity liquid sample.The method of testing of the repairing performance to lead-acid battery increasing longevity liquid is completely with described in embodiment 1.The test result that the lead-acid battery of the present embodiment is increased to longevity liquid is as shown in table 9 below:
Table 9
Result shows, the capacity that increases the waste lead acid battery after longevity liquid reparation through the lead-acid battery of the present embodiment improves approximately 24%.
Embodiment 10:
It is aqueous phase system that the lead-acid battery of the present embodiment increases longevity liquid, by gross mass mark 100%, comprises Graphene 0.05%, carbon nano-fiber 0.05%, carbon nano powder 0.05%, alum 1.8%, magnesium nitrate 4.3% and tetrabutylammonium iodide 5%, and surplus is water.By Graphene, Nano carbon fibers peacekeeping carbon nano powder, with the nitration mixture (volume proportion is 3:1) of red fuming nitric acid (RFNA) and red fuming nitric acid (RFNA), under 30 ℃ of conditions, process 0.1 hour, after processing, solution is cleaned with clear water, under 110 degree conditions, dry 3 hours.Again by Graphene, Nano carbon fibers peacekeeping carbon nano powder sample dispersion after drying in the aqueous solution, add successively alum, magnesium nitrate and tetrabutylammonium iodide, at ambient temperature, agitating heating 2 hours, then at room temperature ultrasonic processing 3 hours, ultrasonic power 300W, obtains lead-acid battery and increases longevity liquid sample.The method of testing of the repairing performance to lead-acid battery increasing longevity liquid is completely with described in embodiment 1.The test result that the lead-acid battery of the present embodiment is increased to longevity liquid is as shown in table 10 below:
Table 10
Result shows, the capacity that increases the waste lead acid battery after longevity liquid reparation through the lead-acid battery of the present embodiment improves approximately 4%.
Embodiment 11:
It is aqueous phase system that the lead-acid battery of the present embodiment increases longevity liquid, by gross mass mark 100%, comprises carbon nano-tube 2%, Graphene 2%, carbon nano-fiber 5%, carbon nano powder 18%, sodium sulphate 2%, sodium nitrate 1.5% and TBAB 8%, and surplus is water.By carbon nano-tube, Graphene, Nano carbon fibers peacekeeping carbon nano powder, with the nitration mixture (volume proportion is 3:1) of red fuming nitric acid (RFNA) and red fuming nitric acid (RFNA), under 80 ℃ of conditions, process 1.5 hours, after processing, solution is cleaned with clear water, under 110 degree conditions, dry 3 hours.Again by carbon nano-tube, Graphene, Nano carbon fibers peacekeeping carbon nano powder sample dispersion after drying in the aqueous solution, add successively sodium sulphate, sodium nitrate and TBAB, at ambient temperature, agitating heating 2 hours, then at room temperature ultrasonic processing 4 hours, ultrasonic power 300W, obtains lead-acid battery and increases longevity liquid sample.The method of testing of the repairing performance to lead-acid battery increasing longevity liquid is completely with described in embodiment 1.The test result that the lead-acid battery of the present embodiment is increased to longevity liquid is as shown in table 11 below:
Table 11
Result shows, the capacity that increases the waste lead acid battery after longevity liquid reparation through the lead-acid battery of the present embodiment improves approximately 25%.
Claims (8)
1. lead-acid battery increases a longevity liquid, it is characterized in that, it is aqueous phase system that described lead-acid battery increases longevity liquid, by gross mass mark 100%, comprises carbon nanomaterial 0.03～30%, inorganic salts 0～20% and organic additive 0.01～10%, and surplus is water;
Described carbon nanomaterial is a kind of, two kinds or several composition in carbon nano-tube, carbon nano-fiber, nano-carbon powder, acetylene black or Graphene;
Described inorganic salts are a kind of, two kinds or several compositions in sulfate, nitrate or chloride;
Described organic additive is a kind of, two kinds or several composition in poly(ethylene oxide), polyvinyl alcohol, polyvinylpyrrolidone, polycaprolactone, methyl iso-butyl ketone (MIBK), methyl alcohol, ethanol, ethylene glycol, glycerol, isobutanol, TBAB, 4-butyl ammonium hydrogen sulfate or tetrabutylammonium iodide.
2. lead-acid battery claimed in claim 1 increases a preparation method for longevity liquid, it is characterized in that, comprises the following steps:
The formula that increases longevity liquid by lead-acid battery claimed in claim 1 weighs each component, carbon nanomaterial is carried out to surface treatment, then be scattered in aqueous phase system, then added successively inorganic salts and organic additive, stir and carry out obtaining lead-acid battery increasing longevity liquid after ultrasonic processing;
Described carries out surface treatment by carbon nanomaterial, its surface treatment is heat treatment, acid treatment or ammonia corrosion processing, described heat treatment is in air, nitrogen, hydrogen, carbon dioxide or steam atmosphere, under 600～1050 ℃ of conditions, processes 0.1～7 hour; Described acid treatment is the mixture that adopts a kind of, two kinds or several acid in sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, under 30～90 ℃ of conditions, processes 0.1～6 hour; Described ammonia corrosion processing is in ammonia or the mixed atmosphere that contains ammonia, under 600～1100 ℃ of conditions, processes 0.1～8 hour.
3. preparation method according to claim 2, is characterized in that, described sulfate is sodium sulphate, potassium sulfate, copper sulphate, magnesium sulfate, aluminum sulfate, alum, zinc sulfate, ferrous sulfate, ferric sulfate or nickelous sulfate.
4. preparation method according to claim 2, it is characterized in that, described nitrate is sodium nitrate, potassium nitrate, calcium nitrate, magnesium nitrate, aluminum nitrate, zinc nitrate, magnesium nitrate, copper nitrate, ferric nitrate, nickel nitrate, cobalt nitrate, manganese nitrate, cerous nitrate or lanthanum nitrate.
5. preparation method according to claim 2, is characterized in that, described chloride is sodium chloride, potassium chloride, calcium chloride, copper chloride, alchlor, zinc chloride, magnesium chloride, frerrous chloride, iron chloride, nickel chloride, cobalt chloride or manganese chloride.
6. preparation method according to claim 2, is characterized in that, the described mixed atmosphere that contains ammonia is Nitrogen, Ammonia gaseous mixture, the volume proportion 40%/60% of gaseous mixture.
7. preparation method according to claim 2, is characterized in that, described is ultrasonic, and its ultrasound condition is under 25-90 ℃ of condition, ultrasonic processing 0.1-8h.
8. preparation method according to claim 2, it is characterized in that, it is aqueous phase system that described lead-acid battery increases longevity liquid, by gross mass mark 100%, comprise carbon nano-tube 2%, Graphene 2%, carbon nano-fiber 5%, carbon nano powder 18%, sodium sulphate 2%, sodium nitrate 1.5% and TBAB 8%, surplus is water, by carbon nano-tube, Graphene, Nano carbon fibers peacekeeping carbon nano powder, the red fuming nitric acid (RFNA) that is 3:1 by volume ratio and the nitration mixture of red fuming nitric acid (RFNA), under 80 ℃ of conditions, process 1.5 hours, after processing, solution is cleaned with clear water, under 110 degree conditions, dry 3 hours, again by the carbon nano-tube after drying, Graphene, Nano carbon fibers peacekeeping carbon nano powder sample dispersion is in the aqueous solution, add successively sodium sulphate, sodium nitrate and TBAB, at ambient temperature, agitating heating 2 hours, then at room temperature ultrasonic processing 4 hours, ultrasonic power 300W, obtain lead-acid battery and increase longevity liquid.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107799839A (en) * | 2017-09-22 | 2018-03-13 | 深圳市晟腾企业管理有限公司 | A kind of efficiently lead-acid battery repair agent and preparation method thereof |
| CN108183266A (en) * | 2017-12-29 | 2018-06-19 | 北京峥程环保科技有限公司 | The agent of lead-acid accumulator Regeneration and Repair and method for restoring lead-acid battery |
| CN111180805A (en) * | 2019-08-07 | 2020-05-19 | 内蒙古华贵科技开发有限公司 | Waste lead-acid storage battery repairing activator and preparation method thereof |
| CN111509309A (en) * | 2019-02-19 | 2020-08-07 | 广州纳为新材料科技有限公司 | Graphene-containing lead-acid battery repairing agent and preparation method thereof |
| CN111816940A (en) * | 2020-07-17 | 2020-10-23 | 福建煜雄科技有限公司 | Storage battery nano regeneration repairing agent and preparation method thereof |
| CN113437372A (en) * | 2021-06-21 | 2021-09-24 | 河南润祥能源科技有限公司 | Restoration method of retired lead-acid battery, restoration electrolyte and preparation method of restoration electrolyte |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107799839A (en) * | 2017-09-22 | 2018-03-13 | 深圳市晟腾企业管理有限公司 | A kind of efficiently lead-acid battery repair agent and preparation method thereof |
| CN108183266A (en) * | 2017-12-29 | 2018-06-19 | 北京峥程环保科技有限公司 | The agent of lead-acid accumulator Regeneration and Repair and method for restoring lead-acid battery |
| CN111509309A (en) * | 2019-02-19 | 2020-08-07 | 广州纳为新材料科技有限公司 | Graphene-containing lead-acid battery repairing agent and preparation method thereof |
| CN111509309B (en) * | 2019-02-19 | 2022-05-17 | 广州纳为新材料科技有限公司 | Graphene-containing lead-acid battery repairing agent and preparation method thereof |
| CN111180805A (en) * | 2019-08-07 | 2020-05-19 | 内蒙古华贵科技开发有限公司 | Waste lead-acid storage battery repairing activator and preparation method thereof |
| CN111816940A (en) * | 2020-07-17 | 2020-10-23 | 福建煜雄科技有限公司 | Storage battery nano regeneration repairing agent and preparation method thereof |
| CN113437372A (en) * | 2021-06-21 | 2021-09-24 | 河南润祥能源科技有限公司 | Restoration method of retired lead-acid battery, restoration electrolyte and preparation method of restoration electrolyte |
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